KR101792903B1 - Polymers with carbazole structural units - Google Patents

Abstract

[식 중,
Ar¹, Ar², Ar³ 은 각각, 서로 독립적으로, 임의의 원하는 유형의 하나 이상의 라디칼 R 에 의해 치환될 수 있는 아릴 또는 헤테로아릴기이고;
m, o 는, 서로 독립적으로, 0 또는 1 이며;
n 은 1, 2 또는 3 이고;
점선은 중합체에서의 연결을 나타냄];

[식 중,
Ar⁴, Ar⁵, Ar⁷, Ar⁸ 은 각각, 서로 독립적으로, 임의의 원하는 유형의 하나 이상의 라디칼 R 에 의해 치환될 수 있는 아릴 또는 헤테로아릴기이고;
Ar⁶ 은 임의의 원하는 유형의 하나 이상의 라디칼 R 에 의해 치환될 수 있는 아릴 또는 헤테로아릴기이거나, 화학식 Ar⁹-Ar⁹ {상기 Ar⁹ 은 각 경우, 독립적으로, 임의의 원하는 유형의 하나 이상의 라디칼 R 에 의해 치환되거나 서로 연결될 수 있는 아릴 또는 헤테로아릴기임} 의 기를 나타내고;
p 는 1, 2 또는 3 이고;
q 는 0 또는 1 이고;
점선은 중합체에서의 연결을 나타냄].The present invention relates to polymers containing at least one carbazole structural unit of formula (I) and at least one arylamine structural unit of formula (II) and / or (III)

[Wherein,
Ar ¹ , Ar ² , Ar ³ are each independently of each other an aryl or heteroaryl group which may be substituted by any desired type of one or more radicals R;
m and o are independently of each other 0 or 1;
n is 1, 2 or 3;
The dotted line indicates the connection in the polymer;

[Wherein,
Ar ⁴ , Ar ⁵ , Ar ⁷ , Ar ⁸ Are each independently of each other an aryl or heteroaryl group which may be substituted by any desired type of one or more radicals R;
Ar ⁶ is an aryl or heteroaryl group that may be substituted by any desired type of one or more radicals R, or is a group of the formula Ar ⁹ -Ar ^9, wherein Ar ⁹ in each case, independently, An aryl or heteroaryl group which may be substituted or linked together by R;
p is 1, 2 or 3;
q is 0 or 1;
The dotted line indicates the connection in the polymer.

Description

[0001] POLYMERS WITH CARBAZOLE STRUCTURAL UNITS [0002]

The present invention relates to polymers having carbazole structural units and processes for their preparation. The invention also relates to formulations and electronic devices comprising said polymers.

The importance of electronic devices including organic, organometallic and / or polymeric semiconductors is increasing: they are used in many commercial products due to cost reasons and performance. Examples that may be mentioned are organic or polymeric light emitting diodes (OLEDs or PLEDs) in organic electroluminescent devices, organic substrate charge-transporting materials (e.g. triarylamine-based hole transporting materials) in photocopiers, organic or polymer light emitting diodes Lt; / RTI > photoconductor. Organic solar cells (O-SC), organic field-effect transistors (O-FET), organic thin film transistors (O-TFT), organic integrated circuits (O-IC), organic optical amplifiers and organic laser diodes (O- Is in the developmental stage of development, and can achieve the major key parts of the future.

Regardless of the article, many electronic devices have the following general layer structure that can be applied to a particular article:

(1)

(2) Electrodes, usually metallic or inorganic, but also made from organic or polymeric conductive materials,

(3) charge-injecting layer (s) or intermediate layer (s) ("planarizing layer"), for example made from a conductive, doped polymer, for example to compensate for electrode heterogeneity,

(4) an organic semiconductor layer,

(5) optionally further charge-transporting, charge-injecting or charge-blocking layers,

(6) The counter electrode, which is the material mentioned in (2)

(7) encapsulation.

The arrangement represents the general structure of an organic electronic device in which the various layers can be combined and in the simplest case the arrangement provides an arrangement in which the organic layer is located between the two electrodes. In this case, the organic layer fulfills all functions including light emission in the case of OLED. Systems of this type are described, for example, in WO 90/13148 A1 based on poly (p-phenylene).

However, the problem that arises in this type of "three-layer system" is the lack of a way to optimize the properties of each component in different layers or the lack of control of charge separation, OLED ") can be solved in a simple manner.

"Small molecule OLEDs" are generally located on a glass substrate, for example, comprising at least one organic hole-injecting layer, a hole-transporting layer, a spinning layer, an electron-transporting layer and an electron-injecting layer and an anode and a cathode . An advantage of this type of multi-layer structure is that the various functions of charge injection, charge transport and radiation can be divided into various layers, so that the properties of each layer can be modified separately. Such modification can significantly improve the performance of electronic devices.

Known electronic devices have useful property profiles. However, it is necessary to continuously improve the properties of such devices. This property particularly includes the lifetime of the electronic device. An additional problem is, in particular, the energy efficiency with which the electronic device will achieve a particular object. In the case of low molecular weight compounds and also organic light emitting diodes which can be described in polymers, the light yield must be particularly high, which means that the lowest possible power must be consumed in order to achieve the specific photocurrent. In addition, the lowest possible voltage for achieving the above-described light emission density is also essential.

The additional object can be considered to provide electronic devices with excellent performance and consistent quality without cost.

In addition, electronic devices can be used or applied for many purposes. In particular, the performance of electronic devices must be maintained over a wide temperature range.

Surprisingly, although not explicitly mentioned, these and additional objects which can be easily derived or deduced from the related discussions discussed in the introductory part of this application are achieved by polymers having all the features of patent claim 1. Advantageous modifications of the polymers according to the invention are protected in the claims dependent on claim 1.

The invention thus relates to polymers containing at least one carbazole structural unit of formula (I) and at least one arylamine structural unit of formula (II) and / or (III)

[Wherein,

Ar ¹ , Ar ² , Ar ³ are each independently of each other an aryl or heteroaryl group which may be substituted by any desired type of one or more radicals R;

m and o are, independently of each other, 0 or 1;

n is 1, 2 or 3;

The dotted line indicates the connection in the polymer;

[Wherein,

Ar ⁴ , Ar ⁵ , Ar ⁷ , Ar ⁸ Are each independently of each other an aryl or heteroaryl group which may be substituted by any desired type of one or more radicals R;

Ar ⁶ is an aryl or heteroaryl group that may be substituted by any desired type of one or more radicals R, or is a group of the formula Ar ⁹ -Ar ^9, wherein Ar ⁹ in each case, independently, An aryl or heteroaryl group which may be substituted or linked together by R;

p is 1, 2 or 3;

q is 0 or 1;

The dotted line indicates the connection in the polymer.

In the carbazole structural units of formula (I), Ar ¹ , Ar ² and Ar ³ are each, independently of one another, 5 to 60, preferably 5 to 20, carbon atoms which may be substituted by any desired type of one or more radicals R And particularly preferably from 5 to 20 ring atoms.

The arylamine structural units of the formula (II) and / or (III) contain the groups Ar ⁴ , Ar ⁵ , Ar ⁷ and Ar ⁸ and are independently of each other substituted by any desired type of one or more radicals R ≪ / RTI > or an aryl or heteroaryl group having from 5 to 60 ring atoms. In formula (II) and / or (III), Ar ⁶ is an aryl group which may be substituted by one or more radicals R of any desired type, or a heteroaryl group, or the formula Ar ⁹ -Ar ⁹ (wherein Ar ⁹ are each Quot; are independently of each other an aryl or heteroaryl group which may be substituted by any desired type of one or more radicals R or which may be linked together. The aryl or heteroaryl groups Ar ⁶ and / or Ar ⁹ contain from 5 to 60 ring atoms.

In the sense of the present invention, aryl groups contain 6 to 60, preferably 6 to 40, particularly preferably 6 to 20 carbon atoms; In the sense of the present invention, the heteroaryl group contains 2 to 59, preferably 2 to 39, particularly preferably 2 to 19 carbon atoms and at least one heteroatom, with the proviso that the sum of carbon atoms and heteroatoms is 5 or more. Preferably, the heteroatom is selected from Si, N, P, O, S and / or Se, with N, O and / or S being particularly preferred. The aryl or heteroaryl group may be substituted by a single aromatic ring, i. E. Benzene, or a simple heteroaromatic ring such as pyridine, pyrimidine, thiophene, or a condensed aryl or heteroaryl group such as naphthalene, anthracene, Phenanthrene, quinoline, isoquinoline, benzothiophene, benzofuran and indole.

For the purposes of the present invention, the radicals Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , Ar ⁷ , Ar ⁸ and / or Ar ³ in the structural units of formulas (I), (II) and / Ar ⁹ is particularly preferably each independently selected from the group consisting of benzene, fluorene, spirobifluorene, cis- and trans-indenofluorene, naphthalene, pyridine, anthracene, phenanthrene, pyrimidine, pyrazine, pyridazine, Benzothiophene, and indole, wherein the benzene, fluorene, spirobifluorene, cis- and trans-indenofluorene, naphthalene, pyridine, anthracene, , Phenanthrene, quinoline and isoquinoline are very particularly preferred.

In the structural unit of the formula (I), (II) and / or (III), R is in each case, independently of one another, F, Cl, Br, I , N (Ar) 2, N (R ') 2, CN P (= O) (Ar) ₂ , P (= O) (R) ₂ , Si (R ') ₃ , B (OR') ₂ , C _{') 2, S (= O} ) Ar, S (= O) R', S (= O) 2 Ar, S (= O) 2 R ', -CR' = CR'Ar, OSO 2 R ', carbon atoms Alkoxy or thioalkoxy groups of from 1 to 40, preferably from 1 to 20, or branched or cyclic alkyl, alkoxy or thioalkoxy groups of from 3 to 40, preferably from 3 to 20, 'may be substituted by, one or more non-adjacent CH ₂ groups R'C = CR' radical R, C≡C, Si (R ' ) 2, Ge (R') 2, Sn (R ') 2, C = O, C = S, C = Se, C = NR ', P (= O) (R'), SO, SO 2, NR , and can be replaced by a ', O, S or CONR', one or more H atom is F, can be replaced with Cl, Br, I, CN or NO _2), or a crosslinkable group, a 5 to 60 aromatic or heteroaromatic ring system having a ring atoms (which each (Which may be substituted with one or more radicals R ') or an aryloxy or heteroaryloxy radical having 5 to 60 ring atoms which may be substituted with one or more radicals R', or a combination of these systems And the two or more substituents R may also form a mono- or polycyclic, aliphatic or aromatic ring system with one another, and R 'in each case independently of each other are H or an aliphatic or aromatic hydrocarbon having 1 to 20 carbon atoms And Ar is an aryl or heteroaryl group having 2 to 30 carbon atoms.

The structural units of formulas (I), (II) and / or (III) may contain one or more crosslinkable groups as described above. "Crosslinkable group" means a functional group capable of reacting irreversibly. As a result, an insoluble cross-linking material is formed. Crosslinking can be supported by heat or UV, microwave, x-ray or electron radiation. Due to the high stability of the polymers according to the invention, less by-products are formed during crosslinking. Also, the crosslinkable groups in the polymers according to the invention are very easily crosslinked, which means that a small amount of energy is required for crosslinking (e.g. <200 ° C for thermal crosslinking).

Examples of crosslinkable groups are units containing double bonds, triple bonds, precursors capable of forming double or triple bonds, or heterocyclic addition-polymerizable radicals. The crosslinkable groups are, inter alia, vinyl, alkenyl, preferably ethenyl and propenyl, C _{4 -20} -cycloalkenyl, azide, oxirane, oxetane, di (hydrocarbyl) amino, cyanate esters, hydroxyl, glycidyl ether, C _{1 -10-in} the alkyl methacrylate, alkenyloxy, preferably ethenyl oxy, perfluoro roal alkenyloxy, preferably perfluoro on-alkyl acrylate, C _{1 -10} ethenyl aryloxy, alkynyl, preferably, maleimide, tri (C _{1 -4)} ethynyl-includes alkylsilyl-alkyl siloxy and tri (C _{1 -4).} Vinyl and alkenyl are particularly preferred.

The aryl or heteroaryl groups Ar ⁴ , Ar ⁵ , Ar ⁶ , Ar ⁷ and Ar ⁸ are not linked to each other through a bond, which means that the unit of formula (II) or (III) And does not indicate a unit. Thus, the unit of formula (II) is a triarylamine structural unit, and the structural unit of formula (III) is usually capable of forming a triarylamine unit in combination with an additional structural unit.

In the sense of the present invention, the aromatic ring system contains 6 to 60, preferably 6 to 40, and particularly preferably 6 to 20 carbon atoms in the ring system. The heteroaromatic ring system in the sense of the present invention contains from 2 to 59, preferably from 2 to 39, and particularly preferably from 2 to 19, carbon atoms and at least one heteroatom in the ring system, The total number of heteroatoms is 5 or more. The heteroatom is preferably selected from Si, N, P, O, S and / or Se. In the sense of the present invention, an aromatic or heteroaromatic ring system is intended to mean a system that does not necessarily contain only an aryl or heteroaryl group, but instead a plurality of aryl or heteroaryl groups may be replaced with a nonaromatic unit (preferably, %), For example sp ³ -hybridized C, N or O atoms. Thus, for example, systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, stilbene may also mean an aromatic ring system in the sense of the present invention And likewise is intended to mean a system in which two or more aryl groups are, for example, blocked by a linear or cyclic alkyl or silyl group. The P = O or C = O group is not usually conjugated-blocking.

An aromatic or heteroaromatic ring system having 5 to 60 ring atoms which may in each case be substituted by any desired radical R and which may be connected to an aromatic or heteroaromatic ring system through any desired position, There can be mentioned benzene, naphthalene, anthracene, phenanthrene, pyrene, chrysene, perylene, fluoranthene, naphthacene, pentacene, benzopyrrene, biphenyl, biphenylene, terphenyl, terphenylene, fluorene, spirobifluorene , Dihydrophenanthrene, dihydropyrenes, tetrahydropyrenes, cis- or trans-indenofluorenes, tolylsenes, isotoluxes, spirotoluxes, spiroisosoluxes, furans, benzofurans, isobenzofurans, dibenzo Benzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6- Quinoline, benzo- Quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthimidazole, phenanthymidazole, pyridimidazole, pyrazine Imidazole, quinoxaline imidazole, oxazole, benzoxazole, naphthoxazole, anthoxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, Diazafiene, 2,3-diazaphylene, 1,6-diazaphylene, 1, 2-diazabicyclene, 1, Diazafilene, 4,5,9,10-tetraazaferylene, pyrazine, phenazine, fluorovin, naphthyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5- Sol, 1,3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole Sol, 1,3,5-tri 1,2,4-triazine, 1,2,3-triazine, tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3 , 5-tetrazine, purine, pteridine, indolizine and benzothiadiazole, benzanthrene, benzanthracene, rubicene and triphenylene. For the purpose of the present invention, particularly preferred are fluorene, spirobifluorene, indenofluorene, anthracene, phenanthrene, dihydrophenanthrene or carbazole.

For purposes of the present invention, an alkyl group having from 1 to 40 carbon atoms (further, each H atom or a CH ₂ group may be substituted with a group described above or a radical R) is preferably a radical methyl, ethyl, Propyl, isopropyl, n-butyl, isobutyl, sec-butyl, , Cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, ethenyl, propenyl, butenyl, pentenyl, cyclo Pentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl or octynyl. The alkoxy group having 1 to 40 carbon atoms is preferably methoxy, trifluoromethoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, Or 2-methylbutoxy.

According to a particularly preferred embodiment of the invention, the polymer according to the invention contains at least one carbazole structural unit of formula (Ia)

[Wherein,

Ar ¹ , Ar ² , Ar ³ are each independently of each other an aryl or heteroaryl group which may be substituted by any desired type of one or more radicals R;

m and o are independently of each other 0 or 1;

The dotted line indicates the connection in the polymer.

The radicals Ar ¹ , Ar ² , Ar ³ and exponents m and o in formula (Ia) have the meanings indicated above for formula (I).

Particularly preferred polymers contain at least one carbazole structural unit of the formula (Ib): &lt; RTI ID = 0.0 &gt;

[Wherein,

Ar ² is in each case independently of each other an aryl or heteroaryl group which may be substituted by any desired type of one or more radicals R,

The dotted line indicates the connection in the polymer.

In formula (Ib), the radical Ar ² has the meanings indicated above for formula (I).

According to a preferred embodiment of the invention, the proportion of carbazole structural units of the formulas (I), (Ia) and (Ib) in the polymer according to the invention is at least 5 mol%, particularly preferably at least 10 mol% Very particularly preferably at least 20 mol% and especially at least 40 mol%.

A surprising advantage can be achieved by using polymers according to the invention which preferably contain one or more arylamine structural units of the formulas (IIa1), (IIa2), (IIIa1) and / or (IIIa2)

[Wherein,

Ar ⁴ , Ar ⁵ , Ar ⁷ , Ar ⁸ Are each independently of each other an aryl or heteroaryl group which may be substituted by any desired type of one or more radicals R;

q is 0 or 1, preferably 1;

R ⁵ represents, in each case independently of each other, a hydrogen atom, a straight chain alkyl of 1 to 40 carbon atoms, an alkoxy or thioalkoxy group or a branched or cyclic alkyl, alkoxy or thioalkoxy group of 3 to 40 carbon atoms or a silyl group or a (-C (= O) NH ₂ ), a haloformyl group (which may be the same or different), a substituted or unsubstituted alkoxy group having 1 to 40 carbon atoms, (-C (= O) -X, X represents a halogen atom), formyl group (-C (= O) -H), isocyanato group, isocyanate group, thiocyanate group or thioisocyanate group, hydroxyl group, nitro group, CF ₃ group, Cl, Br, F, substituted or unsubstituted having a crosslinkable group or a 5 to 60 ring atoms, an aromatic or heteroaromatic ring system, or 5 to 60 having ring atoms An aryloxy or heteroaryloxy group, And the combination of the system, at least one group R ⁵ is mono with a ring bond to each other and / or the group R ⁵ -, or may form a polycyclic, aliphatic or aromatic ring system,

The dotted line indicates the connection in the polymer.

In the formulas (IIa1), (IIa2), (IIIa1) and (IIIa2), the radicals Ar ⁴ , Ar ⁵ , Ar ⁷ and Ar ⁸ and the index q are as described in more detail for the formula (II) and / It has meaning.

It is furthermore desirable to provide a polymer containing at least one arylamine structural unit of the formula (IIIb1) and / or (IIIb2)

[Wherein,

R ⁵ represents, in each case independently of each other, a hydrogen atom, a straight chain alkyl of 1 to 40 carbon atoms, an alkoxy or thioalkoxy group or a branched or cyclic alkyl, alkoxy or thioalkoxy group of 3 to 40 carbon atoms or a silyl group or a (-C (= O) NH ₂ ), a haloformyl group (which may be the same or different), a substituted or unsubstituted alkoxy group having 1 to 40 carbon atoms, (-C (= O) -X, X represents a halogen atom), formyl group (-C (= O) -H), isocyanato group, isocyanate group, thiocyanate group or thioisocyanate group, hydroxyl group, nitro group, CF ₃ group, Cl, Br, F, substituted or unsubstituted having a crosslinkable group or a 5 to 60 ring atoms, an aromatic or heteroaromatic ring system, or 5 to 60 having ring atoms An aryloxy or heteroaryloxy group, And the combination of the system, at least one group R ⁵ is mono with a ring bond to each other and / or the group R ⁵ -, or may form a polycyclic, aliphatic or aromatic ring system,

The dotted line indicates the connection in the polymer.

According to a preferred embodiment of the present invention, in the polymer according to the invention, the arylamine of the formula (II), (IIa1), (IIa2), (III), (IIIa1), (IIIa2), (IIIb1) The proportion of the structural units is at least 5 mol%, particularly preferably at least 10 mol%, very particularly preferably at least 20 mol% and especially at least 40 mol%.

(IIa), (IIa2), (III), (IIIa1), (IIIa2), (IIIb1) and (IIIb2) of the carbazole structural units of formulas (I), (Ia) Is preferably in the range of from 10: 1 to 1:10, particularly preferably in the range of from 5: 1 to 1: 5, and very particularly preferably in the range of from 2: 1 to 1: 2.

Polymers in the sense of the present invention are also intended to mean oligomers and dendrimers.

Oligomer in the sense of the present invention is a term applied to a compound having 3 to 9 repeating units. In the sense of the present invention, a polymer means a compound having at least 10 repeating units. The branching factor of the polymer is 0 (linear polymer, no branch point) to 1 (complete branched dendrimer).

The polymer, oligomer or dendrimer may be conjugated, partially conjugated or non-conjugated. The polymer or oligomer may be linear, branched or dendritic. In a linearly linked structure, the units of formulas (I), (II) and / or (III) may be linked directly to one another or may be linked via a divalent group, for example a substituted or unsubstituted alkylene group, May be linked together through an aromatic or heteroaromatic group. In branched structures, for example, three or more units of formula (I), (II) and / or (III) may be linked via a trivalent or multivalent group, for example via a trivalent or multivalent aromatic or heteroaromatic group To form a branched polymer or oligomer.

The polymers of the present invention preferably have a weight average molecular weight M _w in the range of 10,000 to 200,000 g / mol, particularly preferably in the range of 20,000 to 1,000,000 g / mol and very particularly preferably in the range of 50000 to 500000 g / mol. The weight average molecular weight M _w can be determined by conventional methods, in particular by gel permeation chromatography (GPC).

Polymers according to the invention are prepared using known methods in which the functionalized compounds are copolymerized. The functionalized compound comprises a structural unit of the abovementioned formula and two or more leaving groups such as bromine, iodine, boronic acid or boronic acid ester.

Suitable polymerization reactions are known to the person skilled in the art and are described in the literature. Particularly suitable and preferred polymerization and coupling reactions (all of which produce C-C linkages) are those following Suzuki, Yamamoto, Stille, Heck, Sonogashira or Hiyama. The C-C coupling reaction is particularly preferably carried out via Suzuki coupling.

In particular, remarkable advantages can be achieved by the polymers obtained by the Buchwald reaction. Here, the aromatic diamine is reacted with an aryl halide. Preferred functionalized monomers which can be reacted using a Buchwald reaction are, in particular, halides containing carbazole structural units of formula (I), (Ia) or (Ib) and halides containing structural units of formula (III), (IIIa1) , (IIIb1) or (IIIb2) having two secondary nitrogen atoms.

Thus, preferred carbazole monomers for the preparation of the polymers according to the invention correspond to the following formulas (MI), (MIa) and (MIb)

[Wherein,

Ar ¹ , Ar ² , Ar ³ are each independently of each other an aryl or heteroaryl group which may be substituted by any desired type of one or more radicals R;

m and o are, independently of each other, 0 or 1;

n is 1, 2 or 3;

Z is in each case, independently of one another, a leaving group.

Preferred arylamine monomers for the preparation of the polymers according to the invention are of the formulas (M II), (M IIa1) and (M IIa2);

[Wherein,

Ar ⁴ , Ar ⁵ , Ar ⁷ , Ar ⁸ Are each independently of each other an aryl or heteroaryl group which may be substituted by any desired type of one or more radicals R;

Ar ⁶ is an aryl or heteroaryl group that may be substituted by any desired type of one or more radicals R, or is a group of the formula Ar ⁹ -Ar ^9, wherein Ar ⁹ in each case, independently, An aryl or heteroaryl group which may be substituted or linked together by R;

R ⁵ represents, in each case independently of each other, a hydrogen atom, a straight chain alkyl of 1 to 40 carbon atoms, an alkoxy or thioalkoxy group or a branched or cyclic alkyl, alkoxy or thioalkoxy group of 3 to 40 carbon atoms or a silyl group or a (-C (= O) NH ₂ ), a haloformyl group (which may be the same or different), a substituted or unsubstituted alkoxy group having 1 to 40 carbon atoms, (-C (= O) -X, X represents a halogen atom), formyl group (-C (= O) -H), isocyanato group, isocyanate group, thiocyanate group or thioisocyanate group, hydroxyl group, nitro group, CF ₃ group, Cl, Br, F, cross-linkable group, or an aryl having a substituted or unsubstituted aromatic or heteroaromatic ring system, or 5 to 60 ring atoms having from 5 to 60 ring atoms Oxy or heteroaryloxy group, Systems, wherein one or more groups R &lt; ⁵ &gt; may form a mono- or polycyclic, aliphatic or aromatic ring system with each other and / or with another ring,

p is 1, 2 or 3;

q is 0 or 1;

Z is in each case, independently, a leaving group.

The arylamine monomers of formula (M II) and (M IIa) are polymerized with the carbazole monomers described above, in particular by the Suzuki reaction described above.

In addition, it is particularly preferred to use arylamine monomers of the formula (MIII), (MIIIa1), (MIIa2), (MIIbI) and (MIIb2)

[Wherein,

Ar ⁵ and Ar ⁷ are each independently of each other an aryl or heteroaryl group which may be substituted by any desired type of one or more radicals R;

Ar ⁶ is an aryl or heteroaryl group that may be substituted by any desired type of one or more radicals R, or is a group of the formula Ar ⁹ -Ar ^9, wherein Ar ⁹ in each case, independently, An aryl or heteroaryl group which may be substituted or linked together by R;

R ⁵ represents, in each case independently of each other, a hydrogen atom, a straight chain alkyl of 1 to 40 carbon atoms, an alkoxy or thioalkoxy group or a branched or cyclic alkyl, alkoxy or thioalkoxy group of 3 to 40 carbon atoms or a silyl group or a (-C (= O) NH ₂ ), a haloformyl group (which may be the same or different), a substituted or unsubstituted alkoxy group having 1 to 40 carbon atoms, (-C (= O) -X, X represents a halogen atom), formyl group (-C (= O) -H), isocyanato group, isocyanate group, thiocyanate group or thioisocyanate group, hydroxyl group, nitro group, CF ₃ group, Cl, Br, F, substituted or unsubstituted having a crosslinkable group or a 5 to 60 ring atoms, an aromatic or heteroaromatic ring system, or 5 to 60 having ring atoms An aryloxy or heteroaryloxy group, And the combination of the system, at least one group R ⁵ is mono with one another and / or other ring-may form or polycyclic, aliphatic or aromatic ring system;

p is 1, 2 or 3;

The arylamine monomers of the formulas (MIII), (MIIa1), (MIIa2), (MIIbI) and (MIIb2) are reacted with carbazole monomers, in particular by the above mentioned bacchard reaction.

In addition, the compositions for the preparation of the polymers according to the invention may comprise further reactive compounds, in particular monofunctional compounds, whose molecular weight control is possible. The compound corresponds to the abovementioned monomers but has only one leaving group, preferably bromine, iodine, boronic acid or boronic acid ester groups, instead of two or more leaving groups. In the case of a Buchwald reaction, a monofunctional amine can also be used.

The manner in which polymerization can be carried out by this method and the manner in which the polymer can be separated and purified from the reaction medium are known to those skilled in the art and are described in detail in, for example, WO 03/048225 and WO 04/037887 .

Polymers, oligomers or dendrimers containing structural units according to the invention can be used, for example, as host materials in the preparation of OLEDs or PLEDs, preferably in emitter layers, in particular in the hole-injecting and / or hole-transporting layers do.

The polymer layer can be prepared, for example, by coating from solution, preferably by spin coating.

The invention therefore relates to the use of the polymers, oligomers or dendrimers according to the invention in organic electronic devices.

The organic electronic device is preferably an organic electroluminescent device (OLED), a polymer electroluminescent device (PLED), an organic integrated circuit (O-IC), an organic field effect transistor (O- ), An organic light emitting transistor (O-LET), an organic solar cell (O-SC), an organic optical detector, an organophotoreceptor, an organic field-quench element (O-FQD), a luminescent electrochemical cell (LEC) O-laser).

For the purposes of the present invention, the polymers, oligomers or dendrimers according to the invention are preferably in the form of layers (present in layers) in electronic devices.

The invention therefore also relates to a layer, in particular an organic layer, comprising at least one polymer, oligomer or dendrimer according to the invention as described above.

The polymers and copolymers may additionally be linear or branched. The copolymers according to the invention may have random, alternating or block-like structures or may have alternating arrangements of said plurality of structures. The manner in which copolymers with block-like structures are obtained and additional structural elements are particularly preferred for this purpose are described in detail, for example, in WO 05/014688. This specification is incorporated herein by reference.

In a further embodiment of the invention, the device comprises a plurality of layers. Polymers, oligomers or dendrimers according to the invention can preferably be present in the hole-transport, hole-injecting and / or spinning layers.

The invention therefore also relates to electronic devices comprising at least one hole-transport and / or hole-injecting layer comprising a polymer according to the invention. The thickness of the hole-transporting and / or hole-injecting layer is preferably in the range of 1 to 500 nm, particularly preferably in the range of 2 to 200 nm.

The device may further comprise a layer constructed from a low molecular weight compound (so-called small molecule; referred to as SMOLED). It can be prepared by evaporation of low molecular weight compounds in high vacuum.

In addition, it is preferred to use the polymer as a mixture (blend) with any desired type of additional polymer, oligomer, dendrimer or low molecular weight material, rather than pure material. This can, for example, improve the electronic properties and emit itself. The invention therefore relates to formulations of this type.

In a preferred embodiment of the invention, a polymer, oligomer or dendrimer according to the invention is used as the host material or matrix material in the spinneret. The organic electroluminescent device may comprise one radiation layer or a plurality of radiation layers, wherein the at least one radiation layer comprises one or more polymers, oligomers or dendrimers according to the invention as defined above. When there are a plurality of radiation layers, they preferably have a total of a plurality of radiation maxima from 380 nm to 750 nm, which totally causes white emission, i.e. various radiation compounds capable of emitting fluorescence or phosphorescence are used in the radiation layer . A three-layer system is particularly preferred and the three layers represent blue, green and orange or red emission (in the case of a base structure, see for example WO 05/011013). The white-emitting device is suitable, for example, as illumination or backlighting of a display (LCD).

In addition to these layers, the organic electroluminescent device may also include additional layers, such as in each case at least one hole-injecting layer, a hole-transporting layer, a hole-blocking layer, an electron-transporting layer, an electron-injecting layer, an exciton- Or a charge-generating layer (IDMC 2003, Taiwan; Session 21 OLED (5), T. Matsumoto, T. Nakada, J. Endo, K. Mori, N. Kawamura, A. Yokoi, J. Kido , Multiphoton Organic EL Device Having Charge Generation L ayer). Likewise, for example, an intermediate layer having an exciton-blocking function can be introduced between the two radiation layers. It should be noted, however, that each of the layers does not necessarily have to be present. These layers may likewise comprise polymers, oligomers or dendrimers according to the invention as defined above. It is also possible that a plurality of OLEDs are arranged vertically, which further increases the efficiency for the achieved light yield. In order to increase the coupling-out of light, the last organic layer in the light emitting surface in the OLED can exist in the form of, for example, nanofoams, which reduces the total reflection ratio.

Also preferred is an organic electroluminescent device in which one or more layers are applied using a sublimation method wherein the materials have a pressure of less than 10 ^-5 mbar, preferably less than 10 ^-6 mbar, particularly preferably less than 10 ^-7 mbar Lt; RTI ID = 0.0 &gt; sublimation &lt; / RTI &gt; unit.

Also preferred is an organic electroluminescent device wherein at least one layer is applied with the aid of an OVPD (organic vapor deposition) method or with the aid of carrier gas sublimation, wherein the materials are applied at a pressure of 10 ^-5 mbar to 1 bar do.

In addition, one or more layers may be formed by any desired printing method, such as, for example, by spin coating or by, for example, screen printing, flexographic printing or offset printing, the organic electroluminescent device is preferably applied from a solution by thermal imaging (thermal induced thermal imaging), thermal transfer printing, or inkjet printing. For this purpose, there is a need for soluble compounds obtained through appropriate substitution if necessary.

Correspondingly, the invention also relates to formulations comprising polymers, oligomers or dendrimers as defined above having structural units of the formulas (I), (II) and / or (III) in one or more solvents. The manner in which this type of formulation can be made is known to those skilled in the art and is described, for example, in WO 02/072714, WO 03/019694 and the literature cited herein.

Suitable and preferred solvents are, for example, toluene, anisole, xylene, methylbenzoate, dimethyl anisole, mesitylene, tetralin, veratrol, tetrahydrofuran and chlorobenzene, and mixtures thereof.

The device usually comprises a cathode and an anode (electrode). Electrodes (cathodes, anodes) are selected for the purposes of the present invention in such a manner that their potentials correspond as closely as possible to the potentials of adjacent organic layers to ensure high efficiency electrons or hole injections.

The cathode is preferably a metal complex, a metal having a low work function, a metal alloy, or an alkaline earth metal, an alkali metal, a rare metal or a lanthanide (for example, Ca, Ba, Mg, Al, Yb, and Sm). In the case of a multi-layer structure, additional metals having a relatively high work function, for example Ag, can also be used additionally to the metal, in which case a combination of metals, for example Ca / Ag or Ba / Ag, Is used. It may also be desirable to introduce a thin intermediate layer of material having a high dielectric constant between the metal cathode and the organic semiconductor. For this purpose, for example, alkali metal or alkaline earth metal fluorides, but also corresponding oxides (for example LiF, Li ₂ O, BaF ₂ , MgO, NaF etc.) are suitable. The layer thickness of the layer is preferably 1 to 10 nm, particularly preferably 2 to 8 nm.

The anode preferably comprises a material having a high work function. The anode preferably has a potential of greater than 4.5 eV relative to the vacuum. On the one hand, metals having a high redox potential such as, for example, Ag, Pt or Au are suitable for this purpose. On the other hand, metal / metal oxide electrodes (e.g. Al / Ni / NiO _x , Al / PtO _x ) may also be preferred. For some applications, one or more of the electrodes must be transparent to enable irradiation of organic materials (O-SC) or coupling-out of light (OLED / PLED, O-laser). A preferred structure uses a transparent anode. The preferred anode material here is a conductive mixed metal oxide. Particularly preferred is indium tin oxide (ITO) or indium zinc oxide (IZO). Also preferred are conductive doped organic materials, especially conductive doped polymers such as poly (ethylene dioxythiophene) (PEDOT) or polyaniline (PANI).

The device is correspondingly structured according to the application, provided with a contact and finally sealed, because the lifetime of the device is significantly shortened in the presence of water and / or air.

The present invention will be described in more detail with reference to the following examples, but it is not limited thereto.

Example of work

A) Preparation of monomers

Example  1 (compound 3 of  Produce)

Compound 3 was prepared as follows:

25 g of 4-aminobiphenyl 1 (148 mmol), 22.6 g (72 mmol) of 4,4'-dibromo-biphenyl 2 and 21.4 g of sodium tert-butoxide (222 mmol) was dissolved in toluene and the reaction solution was carefully degassed. The reaction solution was warmed to 80 &lt; 0 &gt; C and the reaction was initiated by the addition of 325 mg (0.36 mmol) Pd ₂ dba ₃ of catalyst and 451 mg (0.73 mmol) BINAP and heating to reflux temperature. The reaction was then allowed to proceed by thin layer chromatography. When the reaction was complete, the mixture was cooled to room temperature and 50 mL of water was added. The phases were separated and the aqueous phase was extracted twice with 50 mL of toluene. It washed three times and the combined organic phase using a 50 ㎖ water, dried over magnesium sulfate (MgSO _4), and the solvent was removed in vacuo. The crude product was recrystallized from toluene.

Example  2 to 4 (compound  8 To 10  of  Produce)

It was prepared as for compound 8 to 10:

The N, N'- di-alkyl di-fluorene-benzidine 8 to 10 were obtained in a manner similar to the synthesis of the dividers-phenyl benzidine (see Example 1).

N, N'-bis (dimethylfluorene) benzidine 8

N, N'-bis (dibutylfluorene) benzidine 9

N, N'-bis (dioctylfluorene) benzidine 10

Example  5 (Compound 16  of  Produce)

Compound 16 was obtained according to the following synthesis sequence:

Phenylcarbazoleboron ester 12 :

150 g (406 mmol) of 3-iodophenylcarbazole 11 were dissolved in 800 ml of dioxane and 123.8 g (488 mol) of bis (pinacolato) diborane and 131.6 g (1.34 mol) of potassium acetate Was added. A solution of 3.2 g (4.1 mmol) of 1,1-bis- (diphenylphosphino) ferrocene palladium (II) chloride (complex with dichloromethane (1: 1), Pd 13%) was then added. The reaction was heated to 110 &lt; 0 &gt; C. The reaction was then allowed to proceed by thin layer chromatography. When the reaction was complete, the batch was cooled to room temperature and 200 mL of water was added. The phases were separated. The organic phase was extracted twice with 100 ml of water. The combined organic phases were washed three times with 100 ml of water, dried with magnesium sulfate, filtered and the solvent was removed in vacuo. The crude product was recrystallized from heptane to give a beige solid.

Bisphenylcarbazole 13:

91 g (242 mmol) of 3-iodophenylcarbazole 11 and 91 g (246 mmol) of phenylcarbazole boron ester 12 were suspended in acetone and 350 ml of a 20% tetraethylammonium hydroxide solution (493 mmol ) Was added and the mixture was carefully degassed using argon. Then 4.6 g (4 mmol) of tetrakis-triphenylphosphine palladium were added. The reaction was heated to 70 &lt; 0 &gt; C. The reaction was then allowed to proceed by thin layer chromatography. When the reaction was complete, the batch was cooled to room temperature and the precipitated product was filtered with suction. The crude product was recrystallized from acetonitrile to give a beige solid.

Diiodobisphenylcarbazole 14:

68 g (139 mmol) of bisphenylcarbazole 13 and 68 g (306 mmol) of N-iodo-succinimide were suspended in glacial acetic acid and stirred overnight at room temperature while the light was blocked. The precipitate was filtered off with suction and washed with water and heptane. The crude product was recrystallized from acetonitrile and a white solid was obtained.

Bisphenylcarbazole bisboron ester 15:

100 g (136 mmol) of diiodobisphenylcarbazole 14 are dissolved in 500 ml of dioxane and 83 g (326 mol) of bis (pinacolato) diborane and 88 g (896 mmol) . 2.2 g (2.7 mmol) of 1,1-bis- (diphenylphosphino) ferrocene palladium (II) chloride (complex with dichloromethane (1: 1), Pd 13%) were then added. The reaction was heated to 110 &lt; 0 &gt; C. The reaction was then allowed to proceed by thin layer chromatography. When the reaction was complete, the batch was cooled to room temperature and 200 mL of water was added. The phases were separated. The organic phase was extracted twice with 100 ml of water. The combined organic phases were washed three times with 100 ml of water, dried with magnesium sulfate, filtered and the solvent was removed in vacuo. The crude product was recrystallized from heptane to give a beige solid.

Bis-3- (4-bromophenyl) bisphenylcarbazole 16:

30 g (41 mmol) of bisphenylcarbazole bisboron ester 15 and 28.8 g (102 mmol) of 1-bromo-4-iodobenzene were dissolved in toluene and 82 ml of 2M sodium carbonate solution (163 mmol) And the mixture was degassed under careful attention under argon. 0.94 g (0.8 mmol) of tetrakistriphenylphosphine palladium was subsequently added. The reaction was heated to 110 &lt; 0 &gt; C. The reaction was then allowed to proceed by thin layer chromatography. When the reaction was complete, the batch was cooled to room temperature and the precipitated product was filtered with suction. The crude product was recrystallized from dimethylformamide (DMF) to give a beige solid.

B) Preparation of polymer

Example  6 and 7: Polymer ( P1  And P2 )

Standard procedure:

2 mmol of the halogenated monomer and 2 mmol of the diamine monomer as well as 0.577 g (6 mmol) of sodium tert - butoxide were dissolved in 20 ml of toluene. The resulting reaction solution was carefully degassed under argon. The solution was warmed to about 80 ° C under a protective gas atmosphere and the reaction was initiated by the addition of 3.6 mg (16 μmol) palladium acetate and 69 mg (96 μmol) of tri- tert - butylphosphine dissolved in 1 ml of toluene Respectively. The reaction mixture was heated at the boiling point for about 1 hour until the solution became sticky. The polymerization was terminated by adding 3 mg of bromobiphenyl and the reaction solution was heated at the boiling point for an additional hour to terminate the last group. The solution was cooled to 65 DEG C and diluted with 80 mL of toluene, 80 mL of 10% thiocarbamide solution was added, and the mixture was stirred at 65 DEG C for 3 hours. The mixture was cooled to room temperature, extracted three times with 50 ml of water, and then precipitated with twice the amount of methanol. For purification, the polymer was dissolved in toluene and then precipitated with twice the amount of methanol. This process was repeated further.

Example  6 (polymer P1 )

Example  7 (polymer P2 )

Comparative Example  8 (comparative polymer V1 )

The preparation of comparative polymer V1 by Suzuki coupling was carried out according to the process described in WO 03/048225.

C) Of PLED  Produce

Example  9 to 14:

Polymer organic light emitting diodes (PLEDs) have already been prepared as described numerous times in the literature (e.g. WO 2004/037887 A2). To illustrate the invention in an exemplary aspect, PLEDs were prepared by spin coating using Polymers P1 and P2 and Comparative Polymer V1.

A typical device has the structure depicted in Fig. 1 (in this structure, the polymer according to the present invention functions as a hole-transporting layer (HTL)). The cathode applied by deposition during the manufacturing process has 4 pixels of 2 x 2 mm. The structure of the device is shown in a plan view in Fig.

In the clean room, the material was washed with deionized water and detergent (Deconex 15 PF) and then activated by UV / ozone plasma treatment. A 80 nm PEDOT layer (PEDOT is a polythiophene derivative (Baytron P VAI 4083 sp.) From H. C. Starck, Goslar supplied as an aqueous dispersion) was then applied by spin coating in the same clean room. The spin speed required is variable (typically 80 nm: 4500 rpm) depending on the dilution and the particular spin-coat structure. To remove residual water in the layer, the material was dried by heating on a hot plate at 180 DEG C for 10 minutes.

Subsequently, under an inert-gas atmosphere (nitrogen or argon), a 20 nm intermediate layer or HTL layer was applied. Polymers according to the invention were processed in this layer from a toluene solution having a concentration of 5 to 8 g / l. A 65 nm spinning layer was then applied from the toluene solution. The two layers were dried by heating at &lt; RTI ID = 0.0 &gt; 180 C &lt; / RTI &gt;

Finally, a Ba / Al cathode was deposited in the pattern indicated through the deposition mask (high purity metal from Aldrich, especially barium 99.99% (order number 474711); deposition unit from Lesker or others, typical vacuum level 5 x 10 ^{& 6} mbar). The device was encapsulated and then characterized, particularly to protect the cathode from air and humid environments.

To this end, the device is clamped in a holder specially made for the substrate size and provided with a spring contact. A photodiode with an ocular response filter can be placed directly in the measurement holder to preclude its effects from exogenous light. A typical measurement setup is shown in FIG.

Typically, the voltage was increased from 0 to a maximum of 20 V by 0.2 V, and then decreased again. For each measurement point, the current through the device and the resulting photocurrent were measured by a photodiode. In this way, IVL data of the test device was obtained. An important characteristic amount is the maximum efficiency measured ("maximum efficiency" to cd / A) and the required voltage for 100 cd / m².

In addition, in order to know the color and correct electroluminescence spectrum of the test device, the voltage required for 100 cd / m &lt; 2 &gt; was applied again after the first measurement and the photodiode was repositioned by the spectral measurement head. It was connected to a spectrometer (Ocean Optics) by optical fibers. The color coordinates (CIE: Commission Internationale de l'Eclairage, standard observer of 1931) can be derived from the measurement spectrum.

 The results obtained using polymers P1 and P2 as well as V1 as an interlayer in the PLED are compiled in Table 1. The used radiation layers EML1 (M1 and E1) and EML2 (M2 and E1) were the combination of the soluble matrix and emitter shown below. The emitter E1 was mixed with the matrix M1 or M2 at a concentration of 20% by weight.

[Table 1]

Example devices for Polymers P1 and P2 (Examples 9, 10, 12 and 13) and Comparative Polymer V1 (Examples 11 and 14) according to the present invention.

Claims (12)

Polymers containing at least one carbazole structural unit of formula (Ia) and at least one arylamine structural unit of formula (II) and / or (III)

[Wherein,
Ar ¹ , Ar ² and Ar ³ are each independently of each other an aryl or heteroaryl group which may be substituted by one or more radicals R;
The radicals R are in each case, independently of one another, F, Cl, Br, I , N (Ar) 2, N (R ') 2, CN, NO 2, Si (R') 3, B (OR ') 2, (= O) R ', P (= O) (Ar) ₂ , P (= O) (R') ₂ , S , S (= O) ₂ Ar, S (= O) ₂ R ', -CR' = CR'Ar, OSO ₂ R ', a straight chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms, Each of which may be substituted with one or more radicals R 'and one or more non-adjacent CH ₂ groups may be replaced by R'C = CR', C≡C, Si (R '), _{2, Ge (R ') 2} , Sn (R') 2, C = O, C = S, C = Se, C = NR ', P (= O) (R'), SO, SO 2, NR ' , O, S or CONR ', and one or more H atoms may be replaced by F, Cl, Br, I, CN or NO ₂ ), a bridging group or an aromatic group having 5 to 60 ring atoms Or a heteroaromatic ring system (which in each case may be substituted with one or more radicals R ') or an aryl having 5 to 60 ring atoms An oxy or heteroaryloxy group which may be substituted with one or more radicals R ', or a combination of the abovementioned groups, and wherein the two or more radicals R also form a mono- or polycyclic, aliphatic or aromatic ring system with one another And R 'in each case independently of one another are H or an aliphatic or aromatic hydrocarbon radical having 1 to 20 carbon atoms and Ar is an aryl or heteroaryl group having 2 to 30 carbon atoms;
m and o are independently of each other 0 or 1;
The dotted line indicates the connection in the polymer;

[Wherein,
Ar ⁴ , Ar ⁵ , Ar ⁷ and Ar ⁸ are each independently of each other an aryl or heteroaryl group which may be substituted by one or more of the radicals R;
Ar ⁶ is an aryl or heteroaryl group which may be substituted by one or more of the radicals R or is a group of the formula Ar ⁹ -Ar ⁹ wherein Ar ⁹ is in each case independently substituted by one or more of the radicals R, Lt; / RTI &gt; is an aryl or heteroaryl group;
p is 1, 2 or 3;
q is 0 or 1;
The dotted line indicates the connection in the polymer. delete A polymer according to claim 1, characterized in that it contains at least one carbazole structural unit of formula (Ib):

Wherein Ar ² and the dotted line have the meanings given in claim 1. The polymer according to claim 1, which comprises at least one arylamine structural unit selected from the group consisting of formulas (IIa1), (IIa2), (IIIa1) and (IIIa2)

[Wherein,
R ⁵ represents, in each case independently of each other, a hydrogen atom, a straight chain alkyl of 1 to 40 carbon atoms, an alkoxy or thioalkoxy group or a branched or cyclic alkyl, alkoxy or thioalkoxy group of 3 to 40 carbon atoms or a silyl group or a (-C (= O) NH ₂ ), a haloformyl group (which may be the same or different), a substituted or unsubstituted alkoxy group having 1 to 40 carbon atoms, (-C (= O) -X, X represents a halogen atom), formyl group (-C (= O) -H), isocyanato group, isocyanate group, thiocyanate group or thioisocyanate group, hydroxyl group, nitro group, CF ₃ group, Cl, Br, F, substituted or unsubstituted having a crosslinkable group or a 5 to 60 ring atoms, an aromatic or heteroaromatic ring system, or 5 to 60 having ring atoms An aryloxy or heteroaryloxy group, And the combination of the system, at least one group R ⁵ is mono with a ring bond to each other and / or the group R ⁵ -, or may form a polycyclic, aliphatic or aromatic ring system,
Ar ⁴ , Ar ⁵ , Ar ⁷ , Ar ⁸ , q and the dotted line have the meanings given in claim 1]. A polymer according to claim 4, characterized in that it contains one or more arylamine structural units of the formula (IIIb1) and / or (IIIb2)

[Wherein,
R ⁵ represents, in each case independently of each other, a hydrogen atom, a straight chain alkyl of 1 to 40 carbon atoms, an alkoxy or thioalkoxy group or a branched or cyclic alkyl, alkoxy or thioalkoxy group of 3 to 40 carbon atoms or a silyl group or a (-C (= O) NH ₂ ), a haloformyl group (which may be the same or different), a substituted or unsubstituted alkoxy group having 1 to 40 carbon atoms, (-C (= O) -X, X represents a halogen atom), formyl group (-C (= O) -H), isocyanato group, isocyanate group, thiocyanate group or thioisocyanate group, hydroxyl group, nitro group, CF ₃ group, Cl, Br, F, substituted or unsubstituted having a crosslinkable group or a 5 to 60 ring atoms, an aromatic or heteroaromatic ring system, or 5 to 60 having ring atoms An aryloxy or heteroaryloxy group, And the combination of the system, at least one group R ⁵ is mono with a ring bond to each other and / or the group R ⁵ -, or may form a polycyclic, aliphatic or aromatic ring system,
The dotted line indicates the connection in the polymer. delete A process for the production of a polymer according to any one of claims 1 to 5, characterized in that the monomer composition is polymerized by a Suzuki or Bukbalt process. A formulation comprising a polymer according to any one of claims 1 and 5 in one or more solvents. An electronic device comprising a polymer according to any one of claims 1 to 5. 10. An electronic device according to claim 9, wherein the polymer is present in the device as a part of a hole-transport or hole-injecting layer. 10. The method of claim 9, wherein the electronic device is an organic electroluminescent device (OLED), a polymer electroluminescent device (PLED), an organic integrated circuit (O-IC), an organic field effect transistor (O-FFT), an organic light emitting transistor (O-LET), an organic solar cell (O-SC), an organic optical detector, an organophotoreceptor, an organic field- Diode (O-laser). A process as claimed in any one of claims 1 to 3, characterized in that at least one layer comprising a polymer according to any one of claims 1 and 5 is applied to the substrate from a solution or by a printing process. 5. A method of producing an electronic device comprising a polymer according to any one of claims 1 to 5.

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